Novel fragrance materials

ABSTRACT

Perfume and fragrance compositions containing the ketone 2,5,5 trimethylacetylcycloheptane which imparts thereto long-lasting tobacco, musky-sweaty, tea-like, woody and orris notes.

United States Patent Hall et al. Mar. 4, 1975 NOVEL FRAGRANCE MATERIALSOTHER PUBLICATIONS [75] Inventors: John B. Hall, Rumson, Ni; Edward J.Shuster, Brooklyn, NY. Chem. Abstr., Vol. 70, 1969, 32946 Z.

G t 1., Z. Ch .8, 424-425 1968 [73] Assignee: International Flavors &Fragrances 6 a em Inc., New York, NY. I P)IHI(II E.\'ammer-Fredertck E.Waddell Flled: P 9, 1973 Attorney, Agent, or FirmArthur L. Liberman,Esq.; 21 App]. No.: 349,180 Harold Hind,

[52 us. Cl. 252/522 ABSTRACT [51] Cljlb Perfume and fragranceCompositions Containing the Fleld 0f Search ..52/5. ketone 2 5 5trimethylacetylcycloheptane which i parts thereto long-lasting tobacco,musky-sweaty, tea- [56] References cued like, woody and orris notes.

UNlTED STATES PATENTS 3.530471 9/1970 Heckert 260/489 4 Clams DrawmgsNOVEL FRAGRANCE MATERIALS BACKGROUND OF THE INVENTION There is acontinuing search for materials having desirable fragrance properties.Such materials are sought either to replace costly natural materials orto provide new fragrances or perfume types which have not heretoforebeen available. Especially desirable qualities for substances havinginteresting fragrances are stability and persistence in a wide varietyof perfumed articles and perfume compositions, ease of manufacture, andintensity of aroma. Thus, British Pat. No. 1,159,188 published on July23, 1969 describes 3,3 dimethyl acetyl cyclohexane having the structure:

as a perfume ingredient having a strong, minty herba' ceous odor". (SeeExample V thereof). Enlarging the ring to seven carbon atoms, adding onemethyl group, and varying the positions of the functional groups on therings has herein been found to give rise to unobvious, unexpected andadvantageous results in the field of perfumery as hereinafter more fullydescribed. It should be noted that the process described in Example V ofBritish Pat. No. 1,159,188 actually produces a mixture which alsocontains a compound having the structure:

See Hall and Lala, Cyclization of Dimethyl-l,6- OctadienesJ.Org.Chem.37,920 (1972).

THE INVENTION The invention comprises the novel compositions containing2,5,5 trimethylacetyl cycloheptane as well as the novel processes andsteps of processes according to which such 2,5,5 trimethylacetylcycloheptane is manufactured, the specific embodiments of which aredescribed hereinafter by way of example and in accordance with which itis now preferred to practice the invention.

Briefly, the present invention provides the ketone 2,5,5 trimethylacetylcycloheptane having the formula:

in perfume and fragrance-modifying materials. The ketone is obtained byhydrogenation of 4 aacetyl-2- carene as more fully described in ExampleI, infra.

It has been found that the ketone of this invention possesses tobacco,musky-sweaty, tea-like, woody and orris notes with good intensity andpersistence. This fragrance quality particularly adapts the ketone forincorporation into perfume compositions and fragrancemodifyingcompositions having a desirable musky aroma. It will be appreciated bythose skilled in the art from the present disclosure that the fragrancecharacter of the finished perfume compositions can be tailored tospecific uses, more fully described hereinafter.

The preparation of 2,5,5 trimethylacetyl cycloheptane and its IR curveis set forth in Grimm et al. Z.Chem.8,424-5 (1968).

Purified 2,5,5 trimethylacetyl cycloheptane (herein sometimes calledKetone I) is an olfactory agent and can be incorporated into a widevariety of compositions which will be enhanced by its tobacco,musky-sweaty, tea-like, woody and orris notes. The Ketone 1 can be addedto perfume compositions in its pure form or it can be added to mixturesof materials in fragranceimparting compositions to provide a desiredfragrance character to a finished perfume material. The perfume andfragrance compositions obtained according to this invention are suitablein a wide variety of perfumed articles and can also be used to enhance,modify or reinforce natural fragrance materials. It will thus beappreciated that the Ketone l of this invention is useful as anolfactory agent and fragrance.

The term perfume composition is used herein to mean a mixture ofcompounds, including, for example, natural oils, synthetic oils,alcohols, aldehydes, ketones, esters, lactones, and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the bouquet orfoundationstone of the composition; (b) modifiers which roundoff andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all stages ofevaporation, and substances which retard evaporation; and (d) top-noteswhich are usually low-boiling fresh-smelling materials. Such perfumecompositions of this invention can be used in conjunction with carriers,vehicles, solvents, dispersants, emulsifiers, surface-active agents,aerosol propellants, and the like.

In perfume compositions the individual components contribute theirparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, the Ketone I of this invention can be used to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientof the composition.

The amount of Ketone I of this invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as much as 50% or aslittle as 3.0% by weight of mixtures or compounds of this invention, oreven less can. be used to impart a tobacco-musky odor to soaps,cosmetics and other products. The amount employed will depend on con-INGREDIENT oLAcetyl-Q-Carene (RichtemChemBer. 100,1892-97 (1967 'Alderet a1. E.German Patent 39,693

Structure:

Acetic Acid Palladium (5%) on carbon catalyst shampoos; cosmeticpreparations such as creams, deodorants, hand lotions, sun screens;powders such as talcs, dusting powders, face powder and the like. Whenthe Ketone l of this invention is used in perfumed articles such as theforegoing. it can be used in amounts of 0.1% or lower. Generally, it ispreferred not to use more than about l0% in the finished perfumedarticle, since the use of too much will tend to unbalance the totalaroma and will needlessly raise the cost of the article The followingexamples serve to illustrate embodiments of the invention as it is nowpreferred to practice INGREDIENTS I PARTS:

2,5,5 Trimethylacetyl Cycloheptane 50 Prepared by the process of ExampleI 6,7-Dihydro-l,l,2,3,3-Pentamethyll(5H) Indanone 5 Produced accordingto Prep. A of Swiss Patent 523,962

Cedrol Methyl Ether 5 having the structur Vertofix Coeur 5 (Reactionproduct of Acetic Anhydride and Polyphosphoric acid with AmericanCedarwood Oil (Runeberg, Acta.Chem.Sound-l5,592 (1961) l,3,l,6,7,8-Hexahydrol,6, 6,7,8,8-Hexamethyl 5 it. It will be understoodthat these examples are illustrative and the invention is to beconsidered restricted thereto only as indicated in the appended claims.

EXAMPLE I The following ingredients are introduced into an autoclave:

AMOUNT The autoclave is purged and pressure-checked and the temperatureis brought to 95C. Hydrogen is admitted with agitation over a period ofone hour (50 psig. pressure) until the theoretical amount has beenintrofduced into the autoclave. The reaction mixture so obtained is thenfiltered, washed and distilled at 8587C at 2-3 mm Hg to obtain Ketone l.

The pure 2,5,5 trimethylacetyl cycloheptane has tobacco, musky-sweaty,tea-like, woody and orris notes.

EXAMPLE I] The following mixture is prepared:

Cyclopenta-gamma-Q-benzopyran Grisalva 3 (Produced by the 50% sulfuricacid treatment= of 3Ethyl-l[2,2,Q-Trimethyl Cyclohexene-5- yl-l]hexen-3-ol-b) Cedrenal having the structure: I

Mixture containing primarily Methyl-2,6,10- 5Trimethyl-Q,5,9dodecatrienl-yl-Ketone, produced according to the processof Example I of Canadian Patent.86#,592

Sandalwood E.I. 10

8,9 Epoxy Ccdrano -l0 Addition of the 2,5,5 Trimethylacetyl Cycloheptaneto this woody aroma composition imparts to it a persistent, strongtobacco, musky sweaty note which is highly desirable.

EXAMPLE III Preparation of Soap Composition One hundred grams ofsoapchips are mixed with one gram of the perfume composition of Example IIuntil a substantially homogeneous composition is obtained. The perfumedsoap composition manifests an excellent tobacco musky woody odorcharacter.

EXAMPLE IV Preparation of a Detergent Composition A total of 100 gramsof a detergent powder is mixed with 0. l 5 grams of the perfumecomposition of Example ll until a substantially homogeneous compositionis obtained. This composition has an excellent tobacco musky woody odor.

EXAMPLE V Preparation of a Cosmetic Powder Composition A cosmetic powderis prepared by mixing in a ball mill 100 grams of talcum powder with0.25 gram of the product obtained from the process of Example I. It hasan excellent tobacco musky sweaty odor.

EXAMPLE VI Perfumed Liquid Detergent sess a tobaccomusky fragrance, theintensity increasing with greater concentration of 2,5,5 TrimethylacetylCycloheptane of this invention.

EXAMPLE VII The compound produced by the process of Example I: 2,5,5Trimethylacetyl Cycloheptane is incorporated in a cologne at aconcentration of2.5% in aqueous ethanol; and into a handkerchief perfumeat a concentration of 20% (in aqueous ethanol). A distinct and definitestrong tobacco, musky, sweaty fragrance is imparted to the cologne andthe the handkerchief perfume.

EXAMPLE VIII The composition of Example II is incorporated in a cologneat a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).The use of the 2,5,5 Trimethylacetyl Cycloheptane in the composition ofExample II affords a distinct and definite strong tobacco, musky, sweatynote to the handkerchief perfume and cologne.

What is claimed is:

l. A perfume composition comprising from 3.0% up to 50% by weight ofsaid composition of 2,5,5 trimethylacetylcycloheptane, and a suitableperfume carrier.

2. A perfumed article comprising from 0.1% up to about 10% by weight ofsaid perfumed article of 2,5,5 trimethylacetylcycloheptane, and asuitable perfume carrier.

3. A perfumed article of claim 2 wherein the carrier is selected fromthe group consisting of:

a cosmetic powder; and a mixture of ethanol and water,

4. A cologne comprising about 25% of 2,5,5-trimethylacetylcycloheptanein a solution of 85% ethyl alcohol and 15% water.

1. A PERFUME COMPOSITION FROM 3.0% UP TO 50%
 1. AN ADHESIVE COMPOSITIONCOMPRISING (1) PETROLEUM WAX REINFORCED WITH ETHYLENE OLEFIN COPOLYMERREINFORCING RESIN BY WEIGHT OF SAID COMPOSITION OF 2,5,5TRIMETHYLCETYLCYWHEREIN THE OLEFIN COMONOMER IS C3-C18 ALPHA-OLEFIN ANDOR CLOHEPTANE, AND A SUITABLE PERFUME CARRIER. UNCONJUGATED DIOLEFIN AND(II)AN ADHESION PROMOTING SYSTEM CONSISTING ESSENTIALLY OF: A. A POLARPOLYMERIC ADDITIVE SELECTIVE SELECTED FROM
 1. AN ETHYLENE ORGANIC ESTERCOPOLYMER CONSISTING AT LEAST 85 MOLE PERCENT COPOLYMERIZED ETHYLENE ANDAT LEAST 9.5 MOLE PERCENT OF COPOLYNERIZED VINYL ALCOHOL ESTER OF AC1-C4 SATURATED MONOCARBOXYLIC ACID OR AT LEAST 7 MOLE PERCENT OF ACOPOLYMERIZED C1-C5 SATURATED ALIPHATIC ALCOHOL ESTER OF ACRYLIC ORMETHACRYLIC COPOLYMER
 2. AN ETHYLENE CARBOXYLIC CID OR ANHYDRIDECOPOLYMER CONTAINING AT LEAST 85 MOLE PERCENT COPOLYMERIZED ETHYLENE AND0.15-5 MOLE PERCENT COPOLYMERIZED ACID, OR ACID PARTIAL ESTER WITH C1-C5ALCOHOLS, OR ANHYDRIDE, AND B. A TACKIFYING RESIN SELECTED FROM WOODRESIN OR DERIVATIVES THEREOF, SAID POLAR POLYMERIC ADDITIVE (A) BEINGPRESENT IN AN AMOUNT OF 10-30 PARTS AND SAID TACKIFYING PARTS, BOTHBASED BEING PRESENT IN AN AMOUNT OF 25-50 PARTS, BOTH BASED UPON 100WEIGHT PARTS OF (1).
 2. A perfumed article comprising from 0.1% up toabout 10% by weight of said perfumed article of 2,5,5trimethylacetylcycloheptane, and a suitable perfume carrier.
 3. Aperfumed article of claim 2 wherein the carrier is selected from thegroup consisting of: a cosmetic powder; and a mixture of ethanol andwater.
 4. A cologne comprising about 25% of2,5,5-trimethylacetylcycloheptane in a solution of 85% ethyl alcohol and15% water.